MERCURY EMISSION AND ANALYSIS FROM INDIAN

COALS USED FOR COMBUSTION AND/OR HIGH

TEMPERATURE PROCESSES

Guided By:
Prof. I.M. Mishra
Submitted by:
Soumyodip Das (16JE002690)
B.Tech Chemical Engineering
Second Year Student
 OVERVIEW
• INTRODUCTION
• TRACE MERCURY ANALYSIS BY COLD VAPOUR ATOMIC FLUORESENCE
1.INSTRUMENTATION
2.PROCEDURE
• DETERMINATION OF TOTAL VAPOUR PHASE MERCURY EMISSIONS FROM
STATIONERY SOURCES
1. SAFETY MEASURES
2. EQUIPMENTS AND SUPPLIES
3. REAGENTS AND STANDARDS-CALIBRATION GASES
4. SAMPLE COLLECTION:
5. CALIBRATION & STANDARDIZATION
6. CALCULATIONS AND DATA ANALYSIS
7. METHOD PERFORMANCE
 INTRODUCTION
• Mercury that is discharged to freshwater and marine water resources is being monitored at
lower levels than before. The need for accurate and precise mercury analysis is crucial at
these trace mercury levels.
Some methods for mercury analysis are:

1 .TRACE MERCURY ANALYSIS by COLD VAPOUR ATOMIC FLUORESENCE

2 .Determination of total vapour phase mercury emissions from stationery

sources(Instrumental Analyzer Procedure)
TRACE MERCURY ANALYSIS BY COLD VAPOUR ATOMIC FLUORESENCE

• INSTRUMENTATION: Trace mercury analysis of industrial and municipal

wastewaters is simplified and easily accomplished using Model RA-4300 FG+
Mercury Analyzer . The samples may be loaded into the autosampler either before or
after oxidant quenching , registered in the software , and the RA-4300 FG+ can
quench and analyse up to 80 standards.
• PROCEDURE:
1 .Load 5ml sample in each tube.
2 .For unquenched samples , the RA-4300 FG+ will first quench
and purge free chlorine.
3 .Stannous Chloride is injected into sample tube.
4 .The mercury is directly purged from the sample tube and collected onto
gold trap for EPA1631.
5 .The mercury is desorbed from the gold trap and measured by an atomic
fluorescence detector.
6 .CALIBRATION : The device is calibrated using aqueous mercury standards.
The calibration is typically performed with each batch of samples , but
recalibration of samples is required if 12 hours has passed since performance
verification.
 DETERMINATION OF TOTAL VAPOUR PHASE MERCURY
EMISSIONS FROM STATIONERY
SOURCES(INSTRUMENTAL ANALYZER PROCEDURE)

• It is a procedure for measuring total vapour phase mercury(Hg) emissions from

stationery sources . It is particularly appropriate for performing emissions testing
and for conducting relative accuracy test audits(RATAs) of mercury continuous
emissions monitoring systems and sorbent trap monitoring systems at coal fired
combustion sources.

• This method is used to determine mass concentration of total vapour phase mercury
in flue gas , which represents the sum of elemental mercury(Hg) and mercury in +2
oxidation state(Hg2+).
• SAFETY MEASURES-One should become familiar with safety recommendations in gas
analyzers user’s manual . OSHA regulations concerning use of compressed gas cylinders and
noxious gases may apply.

• EQUIPMENTS AND SUPPLIES-

1.Sample probe made of appropriate materials.
2.Data Recorder , Moisture Management System.
3.Calibration Gas System(S),Dynamic Spiking Port.
4.Sample Gas Delivery , Hg-analyser.
5.Sample Probe , Sample Line , Sampling Pump.
6.Filter or other Particulate Removal Device.
7.Conditioning Equipment.
• REAGENTS AND STANDARDS-CALIBRATION GASES:
1.High-Level Gas-Equal to the selected calibration span.
2.Mid-Level Gas-40 to 60 percent of the calibration span.
3.Low-Level Gas-10 to 30 percent of calibration span.
4.Zero Gas-No detectable Hg.
5.Dynamic Spiking Gas-The exact concentration of the HgCl2 calibration gas
used to perform the pretest dynamic spiking procedure.

• SAMPLE COLLECTION:
• Sample Point:
1. When used for Hg emission test 12 sample points are used.
2. When used for relative accuracy testing of a Hg CEMS , follow sampling
site selection and sampling point layout procedures for gas monitor RATA
testing.
 3.Determination of stratification-If the test results show effluent gas stream to be
unstratified then sampling at fewer points would be required.

• Initial Measurement System Performance Tests:

1.Interference Test-Measurement system should be free of known interference.
2.Calibration Gas Verification-Verifying the concentration of calibration gases.
3.Measurement System Preparation-Assemble , prepare and precondition the
measurement system according to the standard operating procedure.
4.System Calibration Error Test-Conduct a 3-point system calibration error test
using Hg-standards . Then introduce low , mid and high-level calibration gases
in any order in system calibration mode.
5.System Integrity Check-Perform 2-point system integrity check using zero-gas.
6.Measurement System Response Time-Used to find the minimum sampling
point.
7.Dynamic Spiking Test to demonstrate that site specific flue gas matrix does not
affect measurement system.
• Dilution Type Systems-When they are used three important considerations must be
taken into account proper selection of critical orifice size and dilution ratio , high
quality accurate dilution controller used . Difference in molecular weights must be
considered.

• Moisture Correction-If the moisture basis(wet or dry) of the measurements are

different then the moisture content of the gas must be determined and corrected to a
dry basis.

• CALIBRATION & STANDARDIZATION-

The analyser must be calibrated with Hg standards . The initial 3-point
system calibration error test is required.
• CALCULATIONS AND DATA ANALYSIS-
1.SCE={( Cs - Cv )*100} / CS
SCE=System Calibration Error.
Cs=Measured concentration of a calibration gas.
Cv=certified Hg(0) or Hg(Cl)2 of a calibration gas.
CS=Calibration Span.
2 .D=|SCEf-SCEi|
D=Zero or upscale drift.
SCEf=Post run Calibration Drift.
SCEi=Pre run Calibration Drift.
3 .Moisture Correction: Dry basis : Cd=Cw/(1-Bw)
Cd=Hg concentration dry basis.
Cw=Hg concentration under moist condition.
Bw=Moisture content of sample gas.
• 4 . Moisture Correction: Wet basis : Cw=Cd*(1-Bw)
Cd=Hg concentration dry basis.
Cw=Hg concentration under moist condition.
Bw=Moisture content of sample gas.

• 5 .Spike Dilution Factor DF =(Qprobe/Qspike)

=(Ctdir-Ctnative)/(Ctv-Ctnative)
Qprobe=Total flow rate of stack+spike gas.
Qspike =Flow rate of spike gas.
Ctdir =Tracer Gas concentration injected with spike gas.
Ctnative=Measured trace gas concentration.
Ctv =Dilute tracer gas concentration.
• METHOD PERFORMANCE:

• System Calibration Error Test: This applies to 3-point system calibration error tests using
Hg(0).At each calibration gas level tested(low-,mid-,or high-level), the calibration error
must be within 5.0% of the calibration span.

• System Integrity Checks : This applies to pre- and post-run 2-point system integrity checks
using HgCl2 and zero gas . At each calibration gas level tested(zero and mid- or high-level),
the error must be within 5.0% of the calibration span.

• Drift : For each run , the low-level and upscale drift must be less than or equal to 3.0% of the
calibration span . The drift is applicable if the pre- and post-run system integrity check
responses do not differ by more than 0.0003 mg/metrecube.
• Interference Test : For each interference gas(or mixture) the mean difference between
measurement systems responses with and without the interference test gas(es) is
calculated.The response for the analyser used for the test <=3% of calibration span.

• Dynamic Spiking Test : For the pretest dynamic spiking , the mean value of percentage
spiking recovery must be 100(+-)10% . In addition the RSD of individual percentage spike
recovery values from mean <=5%.